Cyclic phosphorous acid esters and process

ABSTRACT

WHEREIN R1 represents an aliphatic, cycloaliphatic, heterocyclic or aromatic radical linked to the nucleus via an oxygen atom, R2 and R3 each represent aliphatic, cycloaliphatic, heterocyclic or aromatic radicals, which may be linked to the nucleus via a bridge atom A selected from the group of oxygen, sulfur, nitrogen, and phosphorus, n is an integer having a value of 0 or 1 if the bridge atom is oxygen and if the bridge atom is sulfur, nitrogen or phosphorus n has a value of 0, 1 or 2, and R4, R5 and R6 each stand for a carboxylic acid ester group.   Novel organic phosphorus compounds containing at least one phosphorus atom, which may be present in the trivalent state, at least two carboxylic acid ester groups and a phosphorus to carbon double linkage prepared by reacting a malonic acid diester with a compound of trivalent phosphorus having directly linked to the phosphorus atom at least two halogen atoms capable of reacting with activated hydrogen atoms. (The reaction malonic acid diethyl ester with phenyl phosphine dichloride and the resulting reaction product are not within the scope of the instant invention). The novel organic phosphorus compounds of the invention are useful as pest controlling agents, as catalyst components and for forming complexes with transition metals and their compounds. The disclosed compounds include derivatives of 1,2diphosphacyclopentene-(5)-one-(4) having the formula:

[ 51 Aug. 1,1972

[54] CYCLIC PHOSPHOROUS AC ESTERS AND PRGCESS [72] Inventors: GunterBergerhoif, Lengsdorf; la

Tihanyi, Bonn; Jurgen Falbe, Dinslaken; Jul-gen Weber; Werner Weisheit,both of Oberhausen-Holten, all of Germany [73] Assignee: RuhrchemieAktiengesellschaft,

Oberhausen-Holten, Germany 22 Filed: Nov. 1, 1968 21 Appl. No.: 772,841

[30] Foreign Application Priority Data Nov. 7, 1967 Germany ..P 16 68623.0

July 15, 1968 Austria ..A 6801/68 [52] U.S. Cl ..260/927 R, 260/968,260/972,

[51] Int. Cl. ..C07i 9/28 [58] Field of Search ..260/927 R, 968, 972

[56] References Cited UNITED STATES PATENTS 3,014,947 12/1961 Birum..260/972 X 3,488,732 1/1970 Heiba et al ..260/927 X PrimaryExaminer-Lewis Gotts Assistant ExaminerRichard L. RaymondAtt0rneyBurgess, Dinklage & Sprung 5 7 ABSTRACT Novel organic phosphoruscompounds containing at least one phosphorus atom, which may be presentin the trivalent state, at least two carboxylic acid ester groups and aphosphorus to carbon double linkage prepared by reacting a malonic aciddiester with a compound of trivalent phosphorus having directly linkedto the phosphorus atom at least two halogen atoms capable of reactingwith activated hydrogen atoms. (The reaction malonic acid diethyl esterwith phenyl phosphine dichloride and the resulting reaction product arenot within the scope of the instant invention).

The novel organic phosphorus compounds of the in vention are useful aspest controlling agents, as catalyst components and for formingcomplexes with transition metals and their compounds.

The disclosed compounds include derivatives of 1,2-diphosphacyclopentene-(S )-one-(4) having the formula:

R5 O=C4-3C/ wherein R represents an aliphatic, cycloaliphatic,heterocyclic or aromatic radical linked to the nucleus via an oxygenatom, R and R each represent aliphatic, cycloaliphatic, heterocyclic oraromatic radicals, which may be linked to the nucleus via a bridge atomA selected from the group of oxygen, sulfur, nitrogen, and phosphorus, nis an integer having a value of 0 or 1 if the bridge atom is oxygen andif the bridge atom is sulfur, nitrogen or phosphorus n has a value of O,l or 2, and R R and R each stand for a carboxylic acid ester group.

20 Claims, No Drawings CYCLIC PHOSPHQROUS ACID 1 PROCESS This inventionrelates to novel organic phosphorus compounds, which contain at leastone phosphorus atom which may be present in the trivalent state, atleast two carboxylic acid-ester groups and a phosphorus to carbon doublelinkage in their molecule and to a method of preparing the same.

In copending US. Pat. Application Ser. No. 765,687 filed Oct. 7, 1968there is described the reaction of malonic acid diethylester withphenylphosphine dichloride in the presence of a basic reacting materialand preferably in the presence of an organic solvent. The resultingphosphorus compound is advantageously separated from the hydrohalogenideof the base by fractional crystallization or extraction.

In accordance with the present invention it has been found that not onlythe two individual compounds hereinbefore mentioned can be reacted, butthat other malonic acid diesters and other compounds of trivalentphosphorus can be successfully reacted to form a novel group ofcompounds.

It thus has been found according to the invention that novel organicphosphorus compounds, containing at least one phosphorus atom, which maybe present in the trivalent state, at least two carboxylic acid estergroups and a phosphorus to carbon double linkage may be prepared byreacting a malonic acid diester with a compound of trivalent phosphorushaving directly linked to the phosphorus atom at least two halogen atomscapable of reacting with activated hydrogen atoms preferably in thepresence of an organic solvent. The reacu'on of malonic aciddiethylester with phenyl phosphine dichloride described in copendingapplication Ser. No. 765,687 and the reaction product thereof isexcluded from the scope of the instant invention.

The malonic acid diesters suitable for use in the process of theinvention include esters of aliphatic, cycloaliphatic, heterocyclic andaromatic alcohols, wherein the aliphatic alcohols employed asesterification components preferably contain one to carbon atoms.Cycloaliphatic alcohols containing five to 20 carbon atoms areparticularly valuable as ester constituents, while heterocyclic alcoholshaving up to 20 carbon atoms and aromatic alcohols having six to 20carbon atoms are preferred.

The hydrogen halide evolved during the conversion is advantageouslycontinuously removed from the reaction mixture by reaction with basicreacting materials. According to a specific embodiment of the invention,the hydrogen halide can also be continuously removed from the reactionmixture by introduction of inert gases.

The reaction is preferably carried out in a reaction medium, whichdissolves the starting materials but in which the reaction product isnot soluble. Hexane has proved to be particularly well suited for thispurpose. If a solvent reaction medium is used, it is removed afiercompletion of the reaction by the conventional method. The remainingresidue is extracted with a suitable solvent, preferably benzene, fromwhich the resulting phosphorus compound can then be easily isolated.

According to another embodiment of the invention the reaction is carriedout in a solvent, which acts to dissolve the starting material as wellas the novel phosphorus compound produced in the reaction. When thislatter procedure is followed, for instance when benzene is used assolvent, the precipitated hydrohalogenide of the base is separated off,washed and the resulting phosphorus compound isolated from the solutionthereby obtained by evaporation and recrystallization.

The reaction may be advantageously carried out at a temperature of fromabout C up to about +60 C. Higher temperatures should only be used inparticular instances, as such higher temperatures often lead toundesirable detours in the reaction course and in several cases favorthe formation of undesired side products. Temperatures of between and 60C, preferably of between 40 and 60 C, are most conveniently used forcarrying out the reaction. The use of increased pressure appears, otherthan in special instances, to be unnecessary.

If basic acting materials are to be used as acceptors for the hydrogenhalide evolved in the reaction, tertiary amines, as for instance,triethylamine or tributylarnine are preferred. The basic acting materialis generally used in an amount sufficient for the bonding of two molesof hydrogen halide.

Although the ratio of the malonic acid diester to the halogen-phosphoruscompound is not critical, it is preferred to react the malonic aciddiester to the halogen phosphorus components in a molar ratio of l 1. Ithas been found to be advantageous to first mix the malonic acid-diesterand the base used for bonding the evolved hydrogen halide and thereafterto add the halogen-phosphorus compound to the resulting mixture in adropwise fashion. According to another suitable procedure the base isintroduced into a mixture of the malonic acid-diester and thehalogen-phosphorus compound in a dropwise fashion.

In accordance with the invention as phosphorus compound, there arepreferably used compounds of trivalent phosphorus containing directlylinked to the phosphorus atom at least two halogen atoms capable ofreacting with activated hydrogen atoms corresponding to the formula: 1

wherein each X represents halogen, preferably chlorine, bromine oriodine, whereby the two X may be the same or diflerent, R represents analiphatic, cycloaliphatic, heterocyclic or aromatic radical, which maybe substituted, the substituent being required to be non-reacting withthe halogen atoms linked to the phosphorus atom under reactionconditions, A represents a bridge atom and namely one of oxygen, sulfur,nitrogen and phosphorus, n is an integer having a value of 0 or 1 wherethe bridge atom is oxygen, and 0, l or 2 where the bridge atom issulfur, nitrogen or phosphorus.

The organic phosphorus compounds prepared according to the process ofthe invention contain at least one phosphorus atom, which may be presentin the trivalent state, a phosphorus to carbon double linkage and atleast two carboxylic acid ester groups. They are obtained by reaction ofmalonic acid-diesters in the presence of a base with compounds oftrivalent phosphorus represented by the formula: 7

wherein each X represents halogen, preferably chlorine, bromine oriodine, wherein the two X may be the same or different, R represents analiphatic,

wherein X and R have the significance as set out above, A represents abridge atom selected from the group of oxygen, sulfur, nitrogen andphosphorus, n is an integer having a value of l or 2 where the bridgeatom is sulfur,

nitrogen or phosphorus.

The novel phosphorus compounds of the invention can also contain, inaddition to a phosphorus atom, which may be present in the trivalentstate, a phosphorus to carbon double linkage and at least two carboxylicacid ester groups, a second phosphorus atom.

In this case, one phosphorus atom can be present in the trivalent stateand one phosphorus atom in the pentavalent state and a phosphorus tocarbon double linkage can be present at the penta-valent atom.

In accordance with the invention the trivalent as well as thepenta-valent phosphorus atom can carry substituents, which may bealiphatic, cycloaliphatic, heterocyclic or aromatic radicals which maybe substituted, the substituents being non-reacting with the halogenatoms linked to the phosphorus atom under the prevailing reactionconditions.

Further in accordance with the invention it has been found that in thenovel organic phosphorus compounds containing at least one phosphorusatom, which may be present in the trivalent state, at least twocarboxylic acid ester groups, a second phosphorus atom, which may bepresent in the penta-valent state and a phosphorus to carbon doublelinkage at the pentavalent phosphorus atom, a phosphorus to phosphoruslinkage between the trivalent and the penta-valent phosphorus atom ispossible, wherein the trivalent as well as the penta-valent phosphorusatom can carry substituents, which may be aliphatic, cycloaliphatic,heterocyclic or aromatic radicals, which in their turn may besubstituted by substituents non-reactive with the halogen atoms linkedto the phosphorus.

In this instance the trivalent as well as the pentavalent phosphorusatom may be part of a five-mem-; bered hetero-cyclic ring.

Included within the scope of the novel compounds of l g g 4 theinvention are the derivatives of 1,2-diphosphacyclopentene-(S )-one-(4)having the formula:

R41- 5 P )n 3 wherein R represents an aliphatic, cycloaliphatic,heterocyclic or aromatic radical linked to the nucleus via an oxygenatom, R and R each represent aliphatic, cycloaliphatic, heterocyclic oraromatic radicals, which may be linked to the nucleus via a bridge atomA selected from the group of oxygen, sulfur, nitrogen, and phosphorus, nis an integer having a value of 0 or 1 if the bridge atom is oxygen andif the bridge atom is sulfur, nitrogen or phosphorus n has a value of 0,l or 2, and R R and R each stand for a carboxylic acid ester group.

Due to the presence of a phosphorus atom having a pair of freeelectrons, the aforesaid compounds are electron donors and therefore arecapable of forming fomplexes with transition metals and compounds of theatter.

The novel compounds prepared by the process of the invention have proveduseful as pest controlling agents, as catalyst components as well asintermediates for use in organic-technical synthesis reactions as forinstance the complexing reactions just noted.

Of particular importance is the oxidation inhibiting efiiciency of thenovel compounds, as is seen from the following comparison.

EXAMPLE A Through 163.3 g n-butyraldehyde, containing dissolved 3.26 gl-tert.-butoxyl ,22-di-( 4'- dimethylaminophenyl1,2-diphospha-cyclopentene- (5 )-one-(4)]-tricarboxylicacid-(3,3,5)-tri-tert.-bu tylester were passed 54 Nl air during 1 hourat ambient temperature.

n-butyrid acid formed:

after 30 minutes 0.33 g

after 60 minutes 0.46 g

EXAMPLE B n-butyric acid formed:

after 30 minutes 1.05 g

after minutes 1.21 g

EXAMPLE C Through 163.3 g n-butyraldehyde containing none of the novelphosphorus compounds of the invention were passed 54 Nl air during onehour at ambient temperature.

For instance a novel phenyl-substituted phosphorus compound is formedwith favorable results if malonic acid diethyl-ester is reacted withphenylphosphine dichloride in presence of a base preferably in anorganic solvent and the phosphorus compound thereby formed is separatedfrom the hydrochloric acid salt of the base by fractionalcrystallization or extraction. Thereby the chemical compoundl-ethoxy-l,2-dipheny1-[ 1 ,2-diphospha-cyclo-pentene-(5)-one-(4)]-tricarboxylic acid-(3,3,5 )-triethylester is formed.

This phenylsubstituted phosphorus compound proved especially useful ascatalyst component.

Furthermore of particular importance is the oxidation inhibitingefficiency as is seen from the following comparison:

Through 159.5 g n-butyraldehyde were passed 31 1 air during 30 minutes,whereby 15.6 g butyric acid were formed.

Under similar conditions but with addition of 3.2 g of l -ethoxy-1,2-diphenyl-[ 1 ,2-diphospha-cyclopentene- (5 )-one-(4) ]-tricarboxylicacid-( 3 ,3 ,5 )-triethy1ester only 2 g butyric acid were formed.

Melting point of the compound: 114 C. The compound is soluble inbenzene, acetone, acetic acid ethylester, but difficult to dissolve inbenzine, ether, alcohol.

6 EXAMPLE 2 35 g N-methylaniline-N-phosphine dichloride and 27 5 gmalonic acid-diethylester were dissolved in 330 ml benzene. 38 gtriethylamine were then added to the resulting solution under a blanketof nitrogen at 50 C. The reaction mixture was stirred for 2 hours andthe precipitated triethylamine hydrochloride was separated off byfiltration. The filtrate was concentrated to about one third of itsvolume and 330 ml absolute ether added thereto. A highly viscous liquidwas separated by Stratification and was decanted from the ether.

Yield 43 g Analysis C l-1, 0,3 1, C H N P Calc. 56.9 6.1 4.75 10.5 Det.56.10 7.14 4.50 9.30 Molecular weight (vapor pressure-osmometricdetermined) Calc.: 590 Det.: 543

EXAMPLE 3 19.3 g p-tolyl-phosphine dichloride and 16.2 g malonic aciddiethylester were dissolved in 200 ml benzene. A solution of 20.2 gtriethylamine in 100 ml benzene was added thereto at 50 C in a nitrogenatmosphere under stirring. After 2 hours any precipitated triethylaminehydrochloride was separated ofi by suction and the resulting filtrateconcentrated. The colorless crystals which remain, were washed withether and 5 recrystallized from absolute methylalcohol.

Melting point 114C Yield 15.4 5 Analysis C m-1 .0 1 C H P Calc. 60.06.12 l 1.05 0 Det. 59.40 6.27 10.88

Molecular weight: (vapor pressure-osmometric determined) Calc. 560 Bet.508

The individual chemical compounds prepared on the It shows theadsorption bands at:

692 cm 1305 cm" EXAMPLE 1 Melting point 114 to 115C Yield 190 3 AnalysisC H O ECI, C H Cl P Calc. 51.9 4.66 11.8 10.3 Det. 50.69 4.72 12.2011.93

Molecular weight (vapor pressure-osmometric determined) Calc. 601 det.558

basis of examples 1 to 4 are designated in the attached Table by thefollowing numbers:

The additional compounds listed in the table were prepared ashereinafter indicated:

0.2 mols triethylamine were added to about 0.1 mol of the compounds asset out in column 1 of the table, dissolved in about a five fold amountby weight benzene, dropwise under a nitrogen atmosphere at 50 C withstirring. Thereafter the reaction mixture was stirred for 2 hours andthe precipitated triethylamine hydrochloride separated off byfiltration. The solvent was distilled 011 and the remaining reactionproduct either washed with ether and recrystallized from absolute methylalcohol or, if it was a liquid, purified according to conventionalmethods.

9 w I!) A list of several intensive adsorption bands in the IR- spectrum[cm"] of the compounds quoted in the table o=oo c-0-ciH; and therespective melting points of these compounds I l (where solid productsare involved) are hereinafter set g P out. 5

Intensive Adsorption Bands Melting Point P in the IR-Spectrum em- 1 [C]C H Q4 1. 1765; 1735; 1635; 1442 114 A. Z wflh 2. 1755; 1720; 1640; 1445114.5 115 v E i: 228; {22g 5 E having a molecular weight of 568 and amelting point of 5. 1765; 17 55; 12 1 1450 75 s5 75 to 85 C. 6. 50;l 5;];l440 7. 1760; 1710; 1630; 1440 125 126 .12'd!phsphacyclpemene (5 one(4) as 8. 1740; 1710; 1650; claimed in claim 1 of the formula: 9. 1770;1710; 1635; 1435 126 13o "z- 1121: 171mm .zz-a 1 12. 1750, 1725; 1650,l5 13. 1740, 1715; 1610; o I

Y I What is claimed is: hm-O7 1. l,Z-diphosphacyclopentene-(S)-one-(4)of the formula: 2O

nic-c-om O=C( CRz H3 0 R LB J mc- OH;

P om-m R5 A ..R1 g having a molecular weight of 676. wherein 7 6l,2-diphosphacyclopentene-(5)-one-( 4) as l d l l R R R and R is each analkoxy group; 0 mm m c m of the formula R; and R is each an alkyl,phenyl, or halo-alkyl aminoor alkyl phenyl radical; o c 0-0-0iHi each Ais oxygen or alkyl substituted imido; and 0 l I each n is zero or one. HC 0 g P with the proviso that when R R R and R are each 5 P ethoxy (A),,R and (A),, R are not each- Hi0r-o-rl* phenyl. 11 o 0 3113 2. l,2,-diphosphacyclopentene-( 5 )-one-(4) as claimed in claim 1, of theformula:

0:0-o-on1. '11, 0=o( c o-0zH. 1 I I A 02 O P H5 0 having a molecularwe1ght of 588 and a melting point of 01 l25l 26 C. CHIP 0 7. l,2-diphosphacyclopentene-(5 )-one-(4) as 41 c ai edjnslaimly i s fotmulafi O=CO-C 2115 having a molecular weight of 601 and melting point of z 1l4l 15 C. 0

3. 1 ,2-diphosphacyclopentene-(5 )-one-(4) as JL claimed in claim 1 ofthe formula:

O=( J0C21I5 H5CzO O=C--COC2H5 4 V 3 O I g CZHFOALC having a molecularweight of 590.

8. l,2-d1phosphacyclopentene-(5)-one-( 4) as C H O NCH; claimed in claim1 of the formula:

2 hwmfi a 41-011 H3 0=0-o-om H 0=c o oo-0H1 A nn 3 ll 0 i having amolecular weight of 618 and a melting point of JL tol2lC.

4. l,2-diphosphacyclopentene-(5)-one-(4) as C \C claimed in claimloftheformula: v H HP having a melting point of 126 to 130 c, and amolecuhaving a melting point of 98 to 100 C and a molecular claimed inclaim 1 of the formula:

having a molecular weight of 560 and a melting point of 1 14 C.

14. Process of producing compounds of the formula:

O=C -R1 =C- --CR2 i A FR Rn O\\ /P a which comprises reacting:

a. a first phosphorus halide of the formula:

b. a second phosphorus halide of the formula:

weight of 644.

10. l,2-diphosphacyclopentene-(5)-one-(4) as v claimed in claim 1 oftheformula:

25 011 O=CO-( JCH CH3 0=C OO(JCH3 CH3 0 I ll 1113 0H3-o0- P-- l CH; 011

i N CH CH; -0 3 H; t was V, M ,e r721 7 having a melting point of 105 to106 C and a molecular weight of 730. v

1 1. 1,2-diphosphacylcopentene-(5 )-one-(4) as claimed in claim 1 of theformula:

0=0 41 0-0211 HBCPOJL; l l) P/ czHa moi-0 c211 having a molecular weightof 436.

12. l,2-diphosphacylcopentene( 5)-one-( 4) as claimed in claim 1 of theformula:

ozc-o-cms 0= c-e-0-om 0 H5( O ll i c) Q! mu,

having a molecular weight of 492.

13. l,2-diphosphacyclopentene-( 5 )-one-(4) as and,

d. a second malonic acid derivative of the formula:

at to +60 C, where:

R,, R, R, and R is each an alkoxy group; Rq and R is each an alkyl,phenyl, or halo, alkyl amino-, or aikyl-phenyl, radical which isnon-reactive with respect to said X; each A is oxygen or alkylsubstituted imido; each n is zero or one; and each X is chlorine,bromine or iodine,

the reactants and a non-solvent for the reaction product.

18. Process as claimed in claim 17, including using hexane as thereaction medium and extracting the reaction product with benzene.

19. Process as claimed in claim 15 wherein said first and secondphosphorus halide are the same, said first and second malonic acidderivatives are the same and said basically reacting compound istriethylamine.

20. Process as claimed in claim 19, wherein the mole ratio of phosphorushalide to malonic acid derivative is 1:1.

Pat- 11K110, '3,( 8l,477 Dated August 1, 1972 11wnw1- S GunterBergerhof'f e t al.

It is certified that. error appears; in the nbovc-identificd patent andthat said Letters Patent are hereby corrected as'shown below:

Col. 2 line 14 change to --0--.

Col. 4', line 40, change "1,22" to -1,2--

Cols.. 7 and 8, in the Table, opposite 593 change "phenyl" tc--diphenyl--.

Col. 10, Claim 7 line 52, attaclr -CH- I to "N"; I

I Col. 11, line 3]., change "-C--OO-C--' to -C-C-OC'-:

i ll H 0 0 0 Z II i Col 11, line r5 change ('3 (2 H to O (I 0 C Col. 11,lines 61 and 62, change O=-'C to II I w o== T ,5 29' H5C' -O fC\\" C l.12 l o ine 5, change C 0 co C 11 Signed and sealed this 9th daj ofJanuary 1973.

EAL) test:

R OBERT'GOTTSCHALK' Commissioner of Patents WARD MLFLETCHERJR. testingOfficer

2. 1,2,-diphosphacyclopentene-(5)-one-(4) as claimed in claim 1, of theformula:
 3. 1,2-diphosphacyclopentene-(5)-one-(4) as claimed in claim 1of the formula:
 4. 1,2-diphosphacyclopentene-(5)-one-(4) as claimed inclaim 1 of the formula:
 5. 1,2-diphosphacyclopentene-(5)-one-(4) asclaimed in claim 1 of the formula: 6.1,2-diphosphacyclopentene-(5)-one-(4) as claimed in claim 1 of theformula:
 7. 1,2-diphosphacyclopentene-(5)-one-(4) as claimed in claim 1of the formula:
 8. 1,2-diphosphacyclopentene-(5)-one-(4) as claimed inclaim 1 of the formula:
 9. 1,2-diphosphacyclopentene-(5)-one-(4) asclaimed in claim 1 of the formula: 10.1,2-diphosphacyclopentene-(5)-one-(4) as claimed in claim 1 of theformula:
 11. 1,2-diphosphacylcopentene-(5)-one-(4) as claimed in claim 1of the formula:
 12. 1,2-diphosphacylcopentene-(5)-one-(4) as claimed inclaim 1 of the formula:
 13. 1,2-diphosphacyclopentene-(5)-one-(4) asclaimed in claim 1 of the formula:
 14. Process of producing compounds ofthe formula:
 15. Process as claimed in claim 14 including reactinghydrogen halide evolved in said reaction with a basically reactingmaterial.
 16. Process as claimed in claim 14 including passing an inertgas sweep through said reaction mixture whereby removing evolvedhydrogen halide therefrom.
 17. Process as claimed in claim 14 carriedout in the presence of a reaction medium which is a solvent for thereactants and a non-solvent for the reaction product.
 18. Process asclaimed in claim 17, including using hexane as the reaction medium andextracting the reaction product with benzene.
 19. Process as claimed inclaim 15 wherein said first and second phosphorus halide are the same,said first and second malonic acid derivatives are the same and saidbasically reacting compound is triethylamine.
 20. Process as claimed inclaim 19, wherein the mole ratio of phosphorus halide to malonic acidderivative is 1:1.